Addition products of methylformamide or succinimide with glyoxal

ABSTRACT

THE INVENTION PROVIDES THE COMPOUNDS N,N&#39;&#39;-DIHYDROXYETHYLENEBIS(METHYLFORMAMIDE), N,N&#39;&#39;-DIHYDROXYETHYLENEBISSUCCINIMIDE, AND N,N&#39;&#39;-(1,2-DIACETOXYETHYLENE)BISSUCCINIMIDE WHICH ARE USEFUL AS TEXTILE FINISHING AGENTS FOR CELLULOSIC FABRICS, IN RESIN APPLICATION, AND IN PHARMACEUTICAL AND ALLIED INDUSTRIES.

United States Patent 3,579,536 ADDITION PRODUCTS OF METHYLFORMAMIDE ORSUCCINIMIDE WITH GLYOXAL Sidney L. Vail and Andrew G. Pierce, In, NewOrleans, La., Clifiord M. Moran, San Gabriel, Calif., and Robert H.Barker, Metairie, La., assignors to the United States of America asrepresented by the Secretary of Agriculture No Drawing. Filed Feb. 23,1966, Ser. No. 529,251

Int. Cl. C07d 27/10 US. Cl. 260326.3 3 Claims ABSTRACT OF THE DISCLOSUREThe invention provides the compoundsN,N-dihydroxyethylenebis(methylformamide),N,N-dihydroxyethylenebissuccinimide, andN,N-(1,Z-diacetoxyethylene)bissuccinimide which are useful as textilefinishing agents for cellulosic fabrics, in resin applications, and inpharmaceutical and allied industries.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the government of the United States ofAmerica.

This invention relates to the preparation of relatively stableN-methylol types of derivatives, many of which may be obtained by theaddition of N-substituted amido type compounds to 'glyoxal. Morespecifically, the present invention relates primarily to the preparationof a new class of compounds of the following general structure:

wherein R is hydrogen, an alkyl group of one to four carbon atoms, or anacyl group of one to four carbon atoms; Y is not hydrogen, but an alkylor acyl group of one to four carbon atoms or part of a cyclic structureas indicated by the dotted lines in Structure I; and X is hydrogen, analkyl group of one to four carbon atoms when Y is an acyl group, or partof a cyclic structure as indicated by the dotted lines in Structure I.As part of a cyclic structure X and Y may contain other functionalgroups such as carbonyl (CO). In addition to compounds of Structure Ithe present invention relates to similar type compounds of the followinggeneral structure:

or: (|)R o CH-CH 0 ll RC-N N-C R (EH-CH OR OR (11) wherein R' ishydrogen or an alkyl group of one to four carbon atoms which may or maynot contain substituent groups such as nitrile, alkoxide, halide, etc.,and R is as described in Structure I. Moreover, the present inventionalso relates to the use of these new classes of compounds as new textilefinishing agents for cellulosic fabrics. In addition, these compoundsmay be used in resin applications, textile finishing, pharmaceutical,and allied industries, or as intermediates in these fields.

The N-substituted amido type compounds, considered to be more promisingfor formation of compounds of Structure I (R H) by addition to glyoxal,are N-substituted formamides, lactams, and imides. Also, related amidoderivatives containing electron withdrawing groups 3,579,536 PatentedMay 18, 1971 on the acyl or N-substituent portions are considered to besatisfactory amido-type compounds to form linear N,N-(1,2-dihydroxyethylene) derivatives similar to those described byStructure I. The amido-type compounds which are considered to beparticularly well suited for addition to glyoxal in this process includeN-methylformamide, 2- pyrrolidone, succinimide, maleimide, diacetamide,hydantoin, phthalimide, e-caprolactam, and similar compounds.

Similarly, compounds of Structure II (R=H) may be considered to beadducts of R'CONHCHOHCI-IOHNHCOR' and glyoxal, or of two moles of R'CONHand two moles of glyoxal. Although the mechanism of formation is notcompletely understood, it is considered that compounds of Structure II(R=H) are formed more readily by use of amides, particularly where R=Hor R' =alkyl groups containing electron withdrawing groups such asnitrile, alkoxide, halide, etc.

It should be obvious to those skilled in the art that the above listingsare intended only as examples and are not meant to limit this inventionto these specific compounds.

The compounds of this invention are considered to be superior to thosedisclosed in the prior art in several respects. The absence of an imidegroup in the molecule removes a site for chemical degradation of themolecule. This proton is generally easily removed by alkali or chlorinewhich normally leads to an unsatisfactory situation, i.e., chlorinedamage when such compounds are used to produce wash-wear finishes forcellulosic fabrics. In addition, compounds of Structure II contain fourhydroxyl groups capable of further modification. Derivatives (esters andethers) of compounds of Structure I and II are described in the examplesbelow.

The compounds of this invention in concentrations of from two to twentyweight percent can be used to treat substantially any hydrophilicfibrous cellulosic material such as cotton, rayon, ramie, jute, and thelike, or blends of such cellulosic material with noncellulosic materialwhich can be impregnated with a liquid, dried, and cured. In addition tobeing employed as the sole methylol agent in the treating solution ofthe present invention, the N-methylol derivatives of this invention mayalso be used in combination with various conventional treating agents toproduce economical and improved cellulosic textile products.

In a typical treatment by the process of this invention, the solutionapplied to the cellulosic material would comprise about 2 to 20 weightpercent of the amide-glyoxal addition product, 0.3 to 3.0 weight percentof suitable catalyst to promote the reaction, and the remainder water.The above percentages are all based upon the weight of the solution. Anycatalyst useful for curing methylolamidetype finishing agents such asmagnesium chloride, zinc nitrate, or other Lewis-type acids may be used.

It is also within the scope of our invention to add minor proportions ofother agents, such as those required to modify the feel or hand of thetreated fabric.

In the process of this invention, the cellulosic material is impregnatedby passing the fabric into and through the treating solution and thenremoving the excess by squeezing between pad rolls until the amount ofsolution retained (pick-up) is about 50 to 100%, preferably about of thedry fabric weight. The fabric is dried, and then heated briefly at anelevated temperature, usually 1 to 3 minutes at to C., to cause reactionof the finishing agent.

The following examples are given by way of illustration and not by wayof limitation of the invention. The detailed procedures given below inthe examples are illustrative, and are not the only or specificconditions for the synthesis of the compounds of this invention or forthe production of an acceptable finished textile. Many varia tions oradditions within these procedures can be made, as will be readilyapparent to those skilled in the art. In the examples all parts andpercentages are by weight and temperatures are in degrees centigradeunless noted otherwise. The fabrics were tested by the followingmethods:

Those described in the test of the American Society for TestingMaterials are:

Wrinkle Recovery, Monsanto Method, D 1295-60T Breaking Strength, D1682-59T The test evaluating the damage caused by retained chlorine isdescribed in American Association of Textile Chemists and Coloristsstandard test method 92-1962 (scorch tes N,N 1,2dihydroxyethylenebis(Z-pyrrolidone): To 85 grams (1 mole) of2-pyrrolidone was added 72.5 grams (0.5 mole) of 40 glyoxal. Onadjusting the solution to an alkaline pH of about eight with 20% sodiumhydroxide, the solution heated to 65 and a precipitate formed. Thesolution was filtered while still warm to produce 74 grams of a dry,crude product. The residue was worked up to yield 10 grams more.Yield=74%. Product was recrystallized from ethanol-water and melted at190-192 with decomposition.

Elemental analyses.-Calcu1ated for C H N O (percent): C, 52.62; H, 7.07;N, 12.27. ound (percent): C, 52.90; H, 7.27; N, 12.15.

Example 2 HiiN-CH-CHNi JH Hz-x ()H (|)H CH3 N,N' 1,2dihydroxyethylenebis(methylforrnamide): To 59 (1 mole) ofmethylformamide was added 73 grams (0.5 mole) of 40% glyoxal. Thesolution was adjusted to a pH of eight with 20% sodium hydroxide. Afterstanding at room temperature for 48 hours, with sodium bicarbonate addedto maintain an alkaline pH of 8-9, the darkened solution was stored atabout 15. In two to four weeks time, two small batches of crystals wereobtained. Recrystallization from ethanol-water and washing with ethanolproduced a white crystalline material which melted at 156-158 withdecomposition starting at 140- 150". On standing the product darkened.Yield=14%. Evaporation of the residue using vacuum increased the yieldto 20%.

Elemental analyses.-Calculated for C -H N O (percent): C, 40.91; H,6.87; N, 15.90. Found (percent): C, 41.05; H, 6.80; N, 15.73.

Example 3 N,N' 1,2 dihydroxyethylenebissuccinimide: Ten grams ofsuccinimide were dissolved in 50 ml. of distilled water. To thissolution were added 13.6 grams of 40% aqueous glyoxal and the solutionwas adjusted to pH 8-9 with dilute sodium hydroxide. Crystallization ofthe product commenced within one hour. After standing for 3 days, thesolution was filtered and the crystals collected were washed 3 timeswith distilled water and 3 times with absolute ethanol and air dried.Product melted at 182.5- 184.5 Yield=24% with no attempt made to work upthe residue.

Elemental analyses.Calculated for C H N O (per- 4 cent): C, 46.88; H,4.72; N, 10.93. Found (percent): C, 46.99; H, 4.78; N, 11.05.

Example 4 N,N' (1,2-dimethoxyethylene)bis(2-pyrrolidone): To 3 grams ofthe product isolated in Example 1 were added 40 milliliters of methanoland one drop of 6 N hydrochloric acid. The solution was refluxed for onehour and the diether isolated by evaporation to dryness. The product,recrystallized from methanol melted at 199-202".

Elemental analyses.--Calculated for C H N O (percent): C, 56.23; H,7.87; N, 10.93. Found (percent): C, 56.35; H, 7.74; N, 10.90.

Example 5 N,N (1,2 diacetoxyethylene)bissuccinimidez To 3 grams of theproduct from Example 3 were added 50 milliliters of acetic anhydride andone drop of concentrated sulfuric acid. After standing at roomtemperature for one hour with no apparent reaction, the mixture washeated slowly to 95 at which point the solids dissolved. The reactionmixture was left standing at room temperature overnight and theprecipitate which formed was filtered 01f. These solids melted at250-260 with decomposition.

Elemental analyses.-Calculated for C H N O (percent): C, 49.41; H, 4.74;N, 8.23. Found (percent): C, 49.10; H, 4.56; N, 8.52.

Example 6 Example 7 2,3,5,6-tetraacetoxy-l,4diformylpiperazine: Amixture of 4 grams of product from Example '6, 90 milliliters of aceticanhydride, and 0.5 milliliter concentrated sulfuric acid was heated at60 for 2 hours. The mixture was filtered while hot, and then it wascooled in ice. The white crystalline product which formed on chillingwas found to melt at 255-25 6 with decomposition.

Elemental analyses.--Calculated for C H N O (percent): C, 44.92; H,4.84; N, 7.48; mol. wt. 374. Found (percent): C, 45.04; H, 4.86; N,7.37; mol. wt. (by 05- mometer) 370.

N,N' 1,2 dihydroxyethylenebismaleimide: Five grams of maleimide weredissolved in 50 ml. of distilled water. To this solution was added 3.73grams of 40% aqueous glyoxal which had been previously made alkaline(pH=8) with sodium bicarbonate. The desired product crystallized soonafter mixing, but additional sodium bi carbonate had to be added tomaintain a pH of about 8. After 24 hours at room temperature the mixturewas filtered. The solid product was washed with distilled water anddried over a desiccant. The product melted at 172- 1735' withdecomposition.

Elemental analyses.Calculated for C H N O (percent): C, 47.63; H, 3.20;N, 11.11. Found (percent): C, 47.58; H, 3.23; N, 11.08.

Example 9 N,N' 1,2 dihydroxyethylenebis(2-pyr1'olidone) prepared asdescribed in Example 1 was used as a crosslinking agent to producewash-wear cotton fabrics. In this process an 8% aqueous solution of thisagent with 1.2% nitric acid and 0.8% magnesium chloride hexahydrate (ascatalysts) was prepared by adding the compounds to water and warming themixture to dissolve the solids.

A textile fabric, 80 x 80 scoured and bleached cotton 0 printcloth, wasimmersed in the solution and the excess liquid removed mechanically. Thefabric was pinned to a frame, dried for 6 minutes at 70, and cured for 1minute at 160 C. All these steps can be conveniently carried out withconventional textile finishing equipment. The treated fabric was washedto remove unreacted materials and was found to possess a crease recoveryangle of 260 (warp plus fill) compared to a crease recovery angle ofabout 155 (warp plus fill) for the untreated fabric. Further, 98% of thestrength of this treated fabric was retained in the scorch test.

When the above example was repeated using 1% zinc nitrate hexahydrate asthe catalyst, satisfactory results were obtained.

6 We claim: 1. N,N' dihydroxyethylenebis(methylformamide). 2.N,N-dihydroxyethylenebissuccinimide. 3. N,N (1,2diacetoxyethylene)bissuccinimide.

References Cited UNITED STATES PATENTS 3,111,522 11/1963 Vail et a1.260268 3,112,155 11/1963 Vail et a1. 8-116.2

OTHER REFERENCES Sidney Lee Vail, Chemical Abstracts, vol. 65, pp. 19,954 (1966).

Sidney L. Vail et al., Chemical Abstracts, vol. 62, pp.

Vail et al., J. Org. Chem. 30(4), 1195-9 (1965), April 1965.

ALEX MAZEL, Primary Examiner 20 J. TOVAR, Assistant Examiner

